Comparison of micrometeorological and two-film estimates of air–water gas exchange for alpha-hexachlorocyclohexane in the Canadian archipelago

The air-sea gas exchange of alpha-hexachlorocyclohexane (α-HCH) in the Canadian Arctic was estimated using a micrometeorological approach and the commonly used Whitman two-film model. Concurrent shipboard measurements of α-HCH in air at two heights (1 and 15 m) and in surface seawater were conducted during the Circumpolar Flaw Lead study in 2008. Sampling was carried out during eight events in the early summer time when open water was encountered. The micrometeorological technique employed the vertical gradient in air concentration and the wind speed to estimate the flux; results were corrected for atmospheric stability using the Monin-Obukhov stability parameter. The Whitman two-film model used the concentrations of α-HCH in surface seawater, in bulk air at 1 and 15 m above the surface, and the Henry's law constant adjusted for temperature and salinity to derive the flux. Both approaches showed that the overall net flux of α-HCH was from water to air. Mean fluxes calculated using the micrometeorological technique ranged from -3.5 to 18 ng m(-2) day(-1) (mean 7.4), compared to 3.5 to 14 ng m(-2) day(-1) (mean 7.5) using the Whitman two-film model. Flux estimates for individual events agreed in direction and within a factor of two in magnitude for six of eight events. For two events, fluxes estimated by micrometeorology were zero or negative, while fluxes estimated with the two-film model were positive, and the reasons for these discrepancies are unclear. Improvements are needed to shorten air sampling times to ensure that stationarity of meteorological conditions is not compromised over the measurement periods. The micrometeorological technique could be particularly useful to estimate fluxes of organic chemicals over water in situations where no water samples are available.     

Influences of natural emission sources (wildfires and Saharan dust) on the urban organic aerosol in Barcelona (Western Mediterranean Basis) during a PM event

The urban air quality in Barcelona in the Western Mediterranean Basin is characterized by overall high particulate matter (PM) concentrations, due to intensive local anthropogenic emissions and specific meteorological conditions. Moreover, on several days, especially in summer, natural PM sources, such as long-range transported Saharan dust from Northern Africa or wildfires on the Iberian Peninsula and around the Mediterranean Basin, may influence the levels and composition of the organic aerosol. In the second half of July 2009, daily collected PM₁₀ filter samples in an urban background site in Barcelona were analyzed on organic tracer compounds representing several emission sources. During this period, an important PM peak event was observed. Individual organic compound concentrations increased two to five times during this event. Although highest increase was observed for the organic tracer of biomass burning, the contribution to the organic aerosol was estimated to be around 6?%. Organic tracers that could be related to Saharan dust showed no correlation with the PM and OC levels, while this was the case for those related to fossil fuel combustion from traffic emissions. Moreover, a change in the meteorological conditions gave way to an overall increase of the urban background contamination. Long-range atmospheric transport of organic compounds from primary emissions sources (i.e., wildfires and Saharan dust) has a relatively moderate impact on the organic aerosol in an urban area where the local emissions are dominating.     

Investigating phosphorus limitation in a fixed bed filter with phosphorus and nitrogen profile measurements

In 2000, the European Union adopted the European Water Framework Directive (WFD) (European Commission, 2000). The WFD focuses on increasingly stringent nutrient standards including ultra low nitrogen (< 2.2 mg N-total/L) and phosphorus concentrations (< 0.15 mg total phosphorus/L) in receiving surface waters and in relevant point sources like wastewater treatment plant (WWTP) effluent. Expansion of WWTPs with advanced post-treatment processes, like effluent filtration, is widely proposed to meet possible future effluent discharge standards. When combining biological nitrate-nitrogen and chemical phosphorus removal in one filter, phosphorus limitation in the denitrifying process may occur. This study investigated where in the filter bed and under which conditions phosphorus limitation occurs. Profile measurements for nitrate, nitrite, and orthophosphorus (PO4-P) combined with chemical oxygen demand (COD) and 02 were conducted. Results showed that the required PO4-P/NOx-N ratio is approximately 0.006 mg/mg after phosphorous precipitation and flocculation. Profile measurements have proven to be an applicable and useful tool. It showed how nitrate and orthophosphorus are removed through the filter bed based on the PO4-P/NOx-N ratio. When orthophosphorus is removed more rapidly and efficiently compared to nitrate, the PO4-P/NOx-N ratio decreases. When PO4-P/NOx-N ratio thresholds are approximately 0.006 mg/mg for a certain period of time and water temperatures varied significantly, orthophosphorus limitation may occur. Changing the filter-bed configuration or decreasing the coagulant dosage can prevent limitation of the denitrifying process because of a phosphorous shortage.     

Particulate matter emission rates from beef cattle feedlots in Kansas-reverse dispersion modeling

Open beef cattle feedlots emit various air pollutants, including particulate matter (PM) with equivalent aerodynamic diameter of 10 microm or less (PM10); however limited research has quantified PM10 emission rates from feedlots. This research was conducted to determine emission rates of PM10 from large cattle feedlots in Kansas. Concentrations of PM10 at the downwind and upwind edges of two large cattle feedlots (KS1 and KS2) in Kansas were measured with tapered element oscillating microbalance (TEOM) PM10 monitors from January 2007 to December 2008. Weather conditions at the feedlots were also monitored. From measured PM10 concentrations and weather conditions, PM10 emission rates were determined using reverse modeling with the American Meteorological Society/U.S. Environmental Protection Agency Regulatory Model (AERMOD). The two feedlots differed significantly in median PM10 emission flux (1.60 g/m2-day for KS1 vs. 1.10 g/m2-day for KS2) but not in PM10 emission factor (27 kg/1000 head-day for KS1 and 30 kg/1000 head-day KS2). These emission factors were smaller than published U.S. Environmental Protection Agency (EPA) emission factor for cattle feedlots.     

Strategies to evaluate biodegradability: application to chlorinated herbicides

The biodegradability of nitrochlorinated (diuron and atrazine) and chlorophenoxy herbicides (2,4-D and MCPA) has been studied through several bioassays using different testing times and biomass/substrate ratios. A fast biodegradability test using unacclimated activated sludge yielded no biodegradation of the herbicides in 24 h. The inherent biodegradability test gave degradation percentages of around 20–30 % for the nitrochlorinated herbicides and almost complete removal of the chlorophenoxy compounds. Long-term biodegradability assays were performed using sequencing batch reactor (SBR) and sequencing batch membrane bioreactor (SB-MBR). Fixed concentrations of each herbicide below the corresponding EC₅₀ value for activated sludge were used (30 mg L^?1 for diuron and atrazine and 50 mg L^?1 for 2,4-D and MCPA). No signs of herbicide degradation appeared before 35 days in the case of diuron and atrazine and 21 days for 2,4-D, whereas MCPA was partially degraded since the early stages. Around 25–36 % degradation of the nitrochlorinated herbicides and 53–77 % of the chlorophenoxy ones was achieved after 180 and 135 days, respectively, in SBR, whereas complete disappearance of 2,4-D was reached after 80 days in SB-MBR.     

Physical Properties, Photo- and Bio-degradation of Baked Foams Based on Cassava Starch, Sugarcane Bagasse Fibers and Montmorillonite

The objectives of this work were to develop biodegradable trays from cassava starch, sugarcane fibers and Na-montmorillonite (Na-MMT) using a baking process and to study the effects of these components on the physical properties, photo- and bio-degradation of the trays. The sample F20 (produced with 20 g fiber/100 g formulation) showed the maximum yield production (100 %). All formulations resulted in well-shaped trays with densities between 0.1941 and 0.2966 g/cm³. The addition of fibers and Na-MMT resulted in less dense and less rigid trays compared to control samples (only starch). The studied processing conditions resulted in good nanoclay dispersion, leading to the formation of an exfoliated structure. The evaluation of the photo-degradation stability of the trays under UV exposure for 336 h showed that a sample produced with a specific combination of fiber and nanoclay (20 g fiber and 5 g nanoclay/100 g formulation) had the highest loss in stress at break (91 %). Biodegradation assays showed that Control trays (starch) and F20 (20 g fiber/100 g formulation) lost a greater percentage of their weight after 90 days of incubation in soil, with losses of up to 85.50 and 82.70 %, respectively.     

Effect of Fiber Surface Treatments on Thermo-Mechanical Behavior of Poly(Lactic Acid)/Phormium Tenax Composites

In the present study, Phormium Tenax fiber reinforced PLA composites were processed by injection molding and twin screw compounding with a fiber content ranging from 10 to 30 wt%. Three surface treatment methods have been used to improve the Phormium Tenax fiber-matrix interfacial bonding that are as follows: (1) aqueous alkaline solution, (2) silane coupling agent, and (3) a combination of alkaline and silane treatment. The mechanical, thermal and morphological properties of the resulting composites were investigated. The results have shown that the moduli of surface treated fiber reinforced composites are lower than the ones obtained for untreated composites (as a consequence of the decrease in fiber modulus caused by the chemical treatments) and no significant increase in strength was observed for any of the composites compared to neat PLA. SEM micrographs of composite fractured surfaces confirmed an improvement in the interfacial strength, which was insufficient nonetheless to significantly enhance the mechanical behavior of the resulting composites. Results from thermogravimetric analysis and differential scanning calorimetry suggest that surface treatment of Phormium affects the ability of PLA to cold crystallize, and the thermal stability of the composites at the different fiber contents was reduced with introduction of alkali and silane treated Phormium fibers.     

Wild tomato leaf extracts for spider mite and cowpea aphid control

Glandular trichomes on the leaves of wild tomato, L. hirsutum f. hirsutum Mull, also known as Solanum habrochaites (Solanaceae), synthesize and accumulate high levels of methyl ketones (MKs). L. hirsutum accession LA 407, having high concentration of MKs, was grown from seeds under greenhouse conditions. Four MKs (2-undecanone, 2-dodecanone, 2-tridecanone, and 2-pentadecanone) were screened for their toxicity to spider mites, Tetranychus urticae Koch and cowpea aphids, Aphis craccivora Koch. The objectives of this investigation were to: (1) develop a bioassay for testing MKs on spider mite and cowpea aphid mortality and (2) compare the efficacies of wild tomato leaf crude extracts and pure standard materials of MKs against spider mite and cowpea aphid mortality. Our results revealed that spider mites are most sensitive to 2-tridecanone (LC₅₀ = 0.08 μmole cm^?2 of treated leaf surface) and least sensitive to 2-undecanone (LC₅₀ = 1.5 μmole cm^?2 of treated leaf surface) 4 h after treatment. Similarly, 2-tridecanone caused greatest mortality (LC₅₀ = 0.2 μmole cm^?2 of treated leaf surface), whereas 2-undecanone caused the lowest morality (LC₅₀ = 0.48 μmole cm^?2 of treated surface) of cowpea aphid. We concluded that all MKs tested in this investigation are toxic to spider mites and aphids. 2-Tridecanone is more effective in killing mites and aphids compared to other MKs. Toxicity of crude extracts, prepared from the leaves of L. hirsutum accession LA 407, to spider mites and cowpea aphids revealed greater mortality compared to a combined mixture of MKs standard material (used at the same concentration as found on LA 407 leaves). This indicates that in addition to MKs, other unidentified compounds in LA 407 leaf extract also have pesticidal properties. Accordingly, leaf extracts of LA 407 could be explored in crop protection, and they might open a new area of MK formulations and discovery of biorational alternatives for pest control in agricultural fields.     

Speciation and persistence of doxycycline in the aquatic environment: Characterization in terms of steady state kinetics

The aim of the present work was to establish the kinetics for the degradation of doxycycline in the aquatic environment with a view to arriving at a kinetic model that can be used to predict the persistence of antibiotic with confidence. The degradation of doxycycline in both water and sediment phases of aquatic microcosm experiments, as well as in distilled water control experiments, was studied over a period of 90 days. An initial 21% loss due to adsorption by the sediment was observed in the microcosm experiment soon after charging. Biphasic zero-order linear rates of degradation, attributed to microbial degradation of the free and sediment or colloidal particle-adsorbed antibiotic, were observed for both water phase (2.3 × 10^?2 and 4.5 × 10^?3 μgg^?1 day^?1) and sediment phase (7.9 × 10^?3 and 1.5 × 10^?3 μgg^?1 day^?1) of the microcosm experiment. The covered distilled water control experiment exhibited a monophasic zero-order linear rate (1.9 × 10^?3 μgg^?1 day^?1) attributed to hydrolysis, while the distilled water experiment exposed to natural light exhibited biphasic liner rates attributed to a combination of hydrolysis and photolysis (2.9 × 10^?3 μgg^?1 day^?1) and to microbial degradation (9.8 × 10^?3 μgg^?1 day^?1). A kinetic model that takes into account hydrolysis, photolysis, microbial degradation as well as sorption/desorption by colloidal and sediment particles is presented to account for the observed zero-order kinetics. The implications of the observed kinetics on the persistence of doxycycline in the aquatic environment are discussed.     

Effect of ozonization in degradation of trifluralin residues in aqueous and food matrices

Abstract

This study investigates the oxidation of trifluralin residues during ozonation in aqueous and food matrices (tomato). Domestic ozonation equipment with average production of 23.9?mg O₃ L^?1 h^?1 was used in the tests. Modern chromatographic systems (SPME-GC-IT/MS/MS and QuEChERS-GC-IT/MS/MS) were applied for extraction and detection of trifluralin residue in fortified samples of ultrapure water, tap water, superficial water and tomato fruit. The samples were submitted to the ozonation process during 0, 5, 10 and 20?min. Treatment at 5?min was able to degrade 71.5% of herbicide trifluralin in surface water. The removal (%) in ultrapure water reached 83.4% after 20?min of ozonation. The degradation of trifluralin in fortified tomato samples (0.025–0.1?mg kg^?1) were conducted with ozonation at 20?min, and it ranged from 84.4 to 92.7%. After treatment, levels of trifluralin in tomato remained within the established MRLs to EU, USEPA and ANVISA (Brazil). The data provided evidence that ozone is effective for removing trace trifluralin from water and foods.